Vinyl and ether containing sulfones

ABSTRACT

CERTAIN COMPOUNDS CONTAINING TWO OR MORE VINYLSULFONYLALKYL GROUPS ATTACHED TO A PLURALITY OF TERTIARY OR QUATERNARY NITROGEN ATOMS AND/OR TO A PLURALITY OF ETHER OXYGEN ATOMS ARE EFFECTIVE GELATIN HARDENERS.

United States Patent (Nice US. Cl. 260-607 A 2 Claims ABSTRACT OF THEDISCLOSURE Certain compounds containing two or more vinylsulfonylalkylgroups attached to a plurality of tertiary or 'quaternary nitrogen atomsand/or to a plurality of ether oxygen atoms are effective gelatinhardeners.

This is a division of Ser. No. 682,641, filed Nov. 13, 1967 now US. Pat.3,490,911, which in turn is a continuation-impart of Ser. No. 488,797,filed Sept 20, 1965, now abandoned.

This invention relates to gelatin compositions in which a hardener hasbeen incorporated, which hardener contains two or morevinylsulfonylalkyl groups. These groups can be attached to a pluralityof tertiary or quaternary nitrogen atoms or to a plurality of etheroxygen atoms or a combination thereof.

Compounds having olefinic linkages have previously been referred to asuseful for gelatin hardeners but nowhere in the prior art is there anyindication that vinylsulfonylalkyl compounds are useful for thispurpose.

One object of our invention is to provide effective hardeners forphotographic gelatin and for gelatin-containing photographic emulsions.Another object of our invention is to provide gelatin hardeners whichare free from undesirable photographic properties and have good watersolubility, low volatility and low physiological activity. Other'objectsof our invention will appear herein.

We have found that compounds containing two or more vinylsulfonylalkylgroups (that is lower alkyl from 1 to 4 carbon atoms) attached to aplurality of tertiary or quaternary. nitrogen atoms and/or a pluralityof ether oxygen atoms are effective hardeners for gelatin and moreparticularly for photographic gelatin. The term photographic gelatin isinterpreted as including gelatin derivatives and physical mixtures ofgelatin and other colloids, such as mixtures of gelatin with compatiblesynthetic polymers exemplified by copolymers of methyl acrylate andacrylic acid or butyl acrylate and acrylic acid and the like. Thesecompounds are effective not only in compositions in which gelatin is thesole vehicle but also where the vehicle is composed of a carboxylatedpolymer such asethyl acrylate-acrylic acid copolymer and butylacrylate-acrylic acid copolymer, for example, or a mixture thereof withgelatin. Some compounds which are useful as hardeners in accordance withthis invention are as follows'where V is used torepresent where m is 1or 2 These compounds are exemplified in the following:

3,642,908 Patented Feb. 15, 1972 voom-Q-omov VOCHzC'CCHzOV CHzOV I and(VOCHgCH2),NR.X-

F and vocnaonir c-vxand In the above R and R' are alkyl of 1-4 carbonsand X" is an anion such as C H SO C10 1 CH OSO A structural formularepresenting compounds useful as hardeners in accordance with ourinvention is as 'follows:

in which n is an integer from 2 to 6; A is or -O; each R is an alkylgroup of 1 to 4 carbon atoms, X is an anion, such as for example C H SOCl'O CH OSO and the like; m is 1 or 2; Z is a polyvalent radical of nvalences such as for example alkylene radicals of from. 1 to 10 carbonatoms which can contain unsaturation or which can be interrupted by anarylene radical, cycloalkylene radical or by simple functional groupssuch as other, sulfur or amide linkages. In addition, Z can combine withother substituents together with nitrogen atoms when present, thusforming a heterocyclic ring such as piperazine, alkyl substitutedpiperazines and the like.

More specifically, other structural formulae are represented as follows:

in which R and R are lower alkyl groups of 1-4 carbon atoms, each m is 1or 2 and R represents an alkylene chain of from 1-10 carbon atoms whichcan contain unsaturation or which can be interrupted by an aryleneradical, a cycloalkylene radical or by simple functional groups such asether, sulfur or amide linkages. In addition, R and both R s togetherwith the two nitrogen atoms can constitute a heterocyclic ring such aspiperazine, alkyl substituted piperazines and the like, and X is anysuitable anion, such as C7H7SO3-, ClO CH OSO and the like.

The hardeners in accordance with our invention, when present in thegelatin composition, exert hardening action, however, for practicalpurposes ordinarily the amount of hardener used would be in the range of05-15%, based on the weight of the gelatin in the compositions.

The compounds described in this application can be used effectively incombination with hardenable materials in general but they are mostadvantageously used with natural or synthetic polymers used as vehiclesor binders in preparing photographic elements. Specific materials whichcan be hardened according to the practice of this invention includehardenable materials such as polymers, for example, gelatin, colloidalalbumin, acid or watersoluble vinyl polymers, cellulose derivatives,proteins, various polyacrylamides, dispersed polymerized vinylcompounds, particularly those which increase the dimensional stabilityof photographic materials as exemplidied by amine-containing polymers ofalkyl acrylates, methacrylates, acrylic acid, sulfoalkyl acrylates ormethacrylates, maleic acid, and the like.

The hardening agents described herein can be used in various kinds ofphotographic emulsions. In addition to being useful in orthochromatic,panchromatic and infrared emulsions, they are also useful in X-ray andother nonoptically sensitized emulsions. They can be added to theemulsions before or after the addition of any optically sensitizing dyeswhich may be used. They are effective in sulfur and gold sensitizedsilver halide emulsions.

The materials hardened in the practice of this invention can be coatedon a wide variety of supports. Typical supports include those generallyemployed for photographic elements as exemplified by cellulose nitratefihn, cellulose acetate film, polystyrene film, polyethyleneterephthalate film, and related films or resinous materials as well asglass, paper, metal, wood, and the like. Supports such as paper that arecoated with ot-olefin polymers, particularly polymers of a-olefinscontaining 2-10 carbon atoms, as for example, polyethylene,polypropylene, ethylene butene copolymers, and the like, can also beemployed.

In addition to the hardening agents disclosed herein, photographicemulsions and elements can also contain additional additives,particularly those known to be beneficial in photographic emulsions, asexemplified by optical sensitizers, speed increasing materials, otherhardeners, plasticizers, and the like, such as those described in Hennand Goffe US. Pat. 3,128,180 issued Apr. 7, 1964.

The emulsions hardened by new compounds can be used in photographicelements intended for color photography and thus may containcolor-forming couplers or used as emulsions to be developed by solutionscontaining couplers or other color-generating materials or emulsions ofthe mixed-packet type.

The silver halides employed in the photographic emulsions include any ofthe photographic silver halides as exemplified by silver bromide, silveriodide, silver chloride, silver chlorobromide, silver chloroiodide, andthe like. The silver halides used can be those which form latent imagespredominantly on the surface of the silver halide grains or those whichform latent images inside the silver halide emulsion.

Hardened emulsions obtained in accordance with this invention and withgelatin or other hardenable hydrophilic .4 colloids may be used invarious diffusion transfer materials.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

The following Examples 1-10 illustrate methods of preparing thesehardening compounds and the tables following Examples 5 and 12 supplydata indicating desirable photographic effects unexpectedly obtainedusing the various hardeners described herein.

EXAMPLE 1 N,N-bis(Z-vinylsulfonylethyl)piperazine A solution of 52 partsof divinyl sulfone in parts of dry chloroform is cooled to 10 C. andadded dropwise thereto with stirring at 10-15 C. is a solution of 17.2parts of anhydrous piperazine in 100 parts of chloroform. A cloudysolution forms which is stirred for 7 hours and then left overnight. Themass is then treated with charcoal and the filtrate obtained isevaporated at reduced pressure on a water bath. The crude product isrecrystallied first from ethyl acetate and then three times from acetonegiving a colorless product having a melting point of l25l26 C.

EXAMPLE 2 N,N'-bis( 2-vinylsulfonylethyl) piperazinebis(methoperchlorate) A solution of 9.7 parts ofN,N'-bis(2-vinylsulfonylethyl)piperazine and 16.7 parts of methylp-toluenesulfonate in 50 parts of acetonitrile is stirred atroomtemperature for two hours and then refluxed overnight. The solution istreated with charcoal and the filtrate is evaporated at reduced pressureon a water bath to /2 volume and poured into ether. An oily precipitateis obtained. This precipitate is washed with ether, dissolved in aminimum amount of water and then treated with a concentrated solution ofabout 20 parts of sodium perchlorate in 10 parts of water. The productis induced to crystallize, is filtered, and then recrystallized from aminimum amount of water. The colorless product obtained melts at 191-192C.

EXAMPLE 3 N,N-bis(2 vinylsulfonylethyl)-N,N-dimethyl-2-butene- 1,4diamine bis(metho-p-toluenesulfonate) (A) and the correspondingbis(methofluoborate) (B) The metho-toluene sulfonate is prepared inessentially the same manner as in the preceding example but usinginstead of N,N'-bis(2-vinylsulfonylethyl) piperazine, N,Nfbis(2vinylsulfonylethyl)-N,N'-dimethyl 2-butene-1,4- diamine. The colorlessproduct designated (A) melts at 235-236" C. Some of the product isconverted to the fluoborate by using aqueous 'fluoboric acid producing acolorless product designated (B) having a melting point of approximately288 C. at which temperature decomposition occurs.

EXAMPLE 4 N,N'-bis (2-vinylsulfonylethyl) -N,N'-dimethylethylenediaminebis(metho-p-toluenesulfonate) This compound having a melting point ofapproximately 197 C. is prepared in the same manner as in the precedingexamples but using N,N-dimethylethylenediamine as the starting material.

EXAMPLE 5 1,2-(bisvinylsulfonylmethoxy)ethane5,8-dioxa-3,lO-dithiadodecane-1,12-dio1 is prepared by the reaction oftwo molar proportions of sodium Z-hydroxyethylmercaptide with1,2-bis(chloromethoxy) ethane in methanol, followed by evaporation ofthe solvent.

The bis-sulfide is oxidized to the disulfone in hydrogen peroxideaccording to the method of H. S. Schultz et al., J. Org. Chem., 28, 1140(1963).

' 1,2 bis(2 chloroethylsulfonylmethoxy)ethane is prepared by adding thedisulfone diol to a large excess of thionyl chloride containing acatalytic amount of N,N- dimethylformamide, at room temperature.Evaporation of the excess thionyl chloride furnishes the crude chloridewhich is dissolved in tetrahydrofuran and treated with two molarproportions of triethylamine at to C. After 24 hours, the triethylaminehydrochloride and solvent are removed to give an oily product of 111.4975. The identity of this product is confirmed by nmr spectroscopyand elemental analysis.

Samples of the compounds prepared in the preceding examples are added toseparate portions of a high-speed silver bromoiodide emulsion which ispanchromatically sensitized with a cyanine dye. Each emulsion sample iscoated on a cellulose acetate film support at a coverage of 459 mg. ofsilver and 1040 milligrams of gelatin per square foot. A sample of eachfilm-coating is exposed on an Eastman 18 sensitometer, processed'forfive minutes in Kodak DK-50 developer, fixed, washed, and dried with thefollowing results.

Fresh tests Percent swell Hardener c0nc., Rel. Devel- Example g./mole Agspeed Gamma Fog oper Fix Wash 2. 4 110 1. 22 13 920 450 780 7. 2 132 1.12 22 820 390 630 14. 4 120 98 28 420 240 330 100 1. 20 11 940 120 1. 2207 700 115 1. 28 05 510 107 1. 27 05 360 100 1. 22 810 4. 8 123 1. 28 18660 14. 4 112 1. 23 18 510 4. 8 123 1. 30 18 720 14. 4 129 1. 30 17 7504. 8 102 1. 30 18 520 14. 4 76 93 08 360 100 1. 32 800 5---. 2.4 49 1.30.10 400 Control 100 1. 55 16 800 EXAMPLE 6 1,2-bis(2-vinylsulfonylethoxy) ethane A few drops of a solution made byreacting sodium with excess ethylene glycol are added to a stirredsolution of 6.2 parts of ethylene glycol in 23.6 parts of freshlydistilled divinyl sulfone stabilized with less than 0.1% ofhydroquinone. A rapid temperature rise indicates reaction is occurring.The reaction temperature is kept below 35 C. and a few crystals ofhydroquinone are added. After 48 hours, the reaction mixture isneutralized with glacial acetic acid and any volatile compounds areremoved under vacuum (0.5 mm., 30 C., five hours) and the mass isfiltered. A product is obtained having an average molecular weight ofapproximately 2%.

EXAMPLE 7 1,4-bis(2-vinylsulfonylethoxy)butane A procedure is effectedin the same manner as the pre ceding example but using 24 parts ofdivinyl sulfone and 9 parts 1,4-butanediol in parts of drydichloromethane as the reaction medium. A liquid product is obtainedhaving an average molecular weight of approximately 227.

EXAMPLE 8 Bis[2-(2-vinylsulfonylethoxy)ethyl]sulfone The proceduredescribed is repeated using parts of divinyl sulfone and 15.4 parts ofbis(2-hydroxyethyl) sultone in 20 parts of dry dimethyl sulfoxide usingsodium ethoxide catalyst. A liquid product is obtained having an averagemolecular weight of approximately 325.

EXAMPLE 9 N,N'-bis [2- (2-vinylsulfonylethoxy) ethyl] urea 25 parts ofdivinyl sulfone and 14.8 parts of N,N-bis(2- hydroxyethyl)urea arereacted in 25 parts of dry acetonitrile and 15 parts of dimethylsulfoxide using sodium ethoxide catalyst. A product is obtained havingan average molecular weight of approximately 384.

EXAMPLE 10 l,14-bis(vinylsulfonyl)-3,6,9,12-tetraoxatetradecane 25 partsof divinyl sulfone and 15 parts of triethylene glycol are reacted togive the product designated herewith. The product obtained has anaverage molecular weight of 309.

EXAMPLE 11 N,N-bis 2-( 2-vinylsulfonylethoxy) ethyl] dimethylammoniump-tosylate The reaction of 23.8 grams of N-methyldiethanolamine and 47.3grams of divinylsulfone in 300 milliliters of acetonitrile containingsodium methoxide as catalyst and 0.1 gram of hydroquinone yields anamine adduct which is quaternized in solution with 37.2 grams of methylptosylate. Isolation by precipitating into ether produces alight-colored oil of 11 1.5310.

EXAMPLE 12 N,N-bis [2- (2-vinylsulfonylethoxy) ethyl] dimethylammoniumperchlorate By treating 21.7 grams of the tosylate of the precedingexample with 6 grams of sodium perchlorate in acetonitrile produces,after filtering and removing of the solvent, a viscous oil in 11,1.4883.

Samples of the compounds prepared in Examples 6-12 are added to separateportions of a high-speed silver bromoiodide emulsion which arepanchromatically sensitized with a cyanine dye. Each emulsion sample iscoated on a cellulose acetate film support at a coverage of 459 mg. ofsilver and 1040 mg. of gelatin per square foot. Samples of the variousfilms are exposed on an Eastman 1B sensitometer, processed for fiveminutes in Kodak Developer DK-SO, fixed, washed, and dried. Theproportions of hardener used, the example from which the hardener wasderived, the photographic tests on the fresh coatings and the percentageof swell as compared with the control are as follows:

Fresh tests Hardener cone. Rel. Percent Example No. (gJmole Ag) speedGamma Fog swell The hardeners in accordance with our invention haveshown themselves to be useful in color photography such as inphotographic emulsions in which color couplers have been incorporated.The use of these hardeners results in reduced stain with no adversesensitometric effects when used in levels producing satisfactoryhardness in contrast with some of the aldehyde types of gelatinhardeners. No adverse effect upon dye hue or stability of the emulsionhas been observed. For instance,

in a photographic product in which coatings of the following structurewere applied to a support these hardeners have been used with goodeffect:

Layer 6-gelatin layer Layer 5--red-sensitive silver chlorobromidegelatin consisting of 90 mole percent bromide and a phenolic cyancoupler of the type described in US. Pat. 2,423,730.

Layer 4gelatin layer and an ultraviolet absorber Layer 3green-sensitivesilver chlorobromide gelatin emulsion consisting of 80 mole percentchloride and a pyrazolone magenta coupler of the types described in US.Pat. 2,600,788.

Layer 2gelatin layer Layer lbluesensitive silver chlorobromide gelatinemulsion consisting of 98 mole percent bromide and an acyl acetanilideyellow coupler of the type described in US. Pat. 2,875,057.

The hardeners in accordance with our invention can be used in all six ofthe layers of the product or they can be used in the emulsioncompositions with other hardeners being used in the gelatin layers ifdesired. In such use improvement in stain is obtained as compared withthe use of a hardener such as formaldehyde or mucochloric acid.

Silver halide emulsions containing the hardeners of the invention can beused in dilfusion transfer processes which utilize the undevelopedsilver halide in non-image areas of the negative to form a positive bydissolving the undeveloped silver halide and precipitating it on asilver layer in close proximity to the original silver halide emulsionlayer. Such processes are described in US. Pats. 2,352,014 of Rottissued June 20, 1944; 2,543,181 of Land issued Feb. 27, 1951; and3,020,155 of Yackel, Yutzy, Foster and Rasch issued Feb. 6, 1962. Theemulsions can also be used in difiusion transfer color processes whichutilize a difiusion transfer of an imagewise distribution of developer,coupler or dye, from a light-sensitive layer to a second layer, whilethe two layers are in close proximity to one another. Such processes aredescribed in Rogers US. Pat. 2,983,606 issued May 9, 1961; Weyerts eta1. U.S. Pat. 3,253,915 issued May 31, 1966; and Whitmore US. Pat.3,227,552 issued Jan. 4, 1966. Silver halide emulsions containing thehardeners of the invention can be processed in stabilization processessuch as the ones described in US. Pat. 2,614,927 of Broughton andWoodward issued Oct. 21, 1952, and as described in the articleStabilization Processing of Films and Papers, by H. D. Russell, E. C.Yackel and J. S. Bruce in P.S.A. Journal, Photographic Science andTechnique, volume 16B, October 1950.

The hardeners of this invention can be used to harden silver halideemulsion and other photographic layers containing silver halidedeveloping agents such as polyhydroxy benzene, amino phenol phenol and3-pyrazolidone developing agents.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

We claim:

1. Bis 2-(2-vinylsulfonylethoxy) ethyl] sulfone.

2. 1,2-bis-(vinylsulfonylmethoxy)ethane.

No references cited.

LEWISGOTTS, Primary Examiner D. R. PHILLIPS, Assistant Examiner US. Cl.X.R.

96-111; 106-12 S; 260-117, 268 R, 345.9, 501.1 S, 553 D, 567.6 B, 584 Rmg I UNITED STATES PATENT oEETcE C RTIFICATE OF CORRECTION Patent No.642 i9 Dated February 1 1972 Inventor) Donald M. Burness Stanley W.Cowan and Charles J. Wrigh It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 2 line 4, "VOCH VOCH CECCH OV Column 2, lines 10-15, "(VOCI-IgCH),NR.X" should read H (VOCH CH NR.X'

C-CCH 0V" should read CH, Column 2, line 15, "and VOCH3CH kV.X-" shouldread 9 R --and VOCH CH NV.X-

H Column 2 line 28 V 1:] (,H C CCH I? V. ZC H7SO CH CH (III-I CH shouldread -"V"I:I-CH2CECCH2'1:I'V.2C7H7SO3- CH CH Column 2, line 56, "other"should read -ether-.

Column 6, line 61, under the Heading "Percent Swell", "480" should read-430-.

Signed and sealed this 5th day of September 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

